CN104138829A - Polyamino acid adjusted and controlled super-hydrophobic surface material constructed in a biomineralization way and the preparation method thereof - Google Patents
Polyamino acid adjusted and controlled super-hydrophobic surface material constructed in a biomineralization way and the preparation method thereof Download PDFInfo
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- CN104138829A CN104138829A CN201310163289.4A CN201310163289A CN104138829A CN 104138829 A CN104138829 A CN 104138829A CN 201310163289 A CN201310163289 A CN 201310163289A CN 104138829 A CN104138829 A CN 104138829A
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- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 42
- 239000000463 material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 230000033558 biomineral tissue development Effects 0.000 title claims abstract description 28
- 239000002253 acid Substances 0.000 title claims abstract description 7
- 239000011521 glass Substances 0.000 claims abstract description 97
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000006259 organic additive Substances 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 239000008367 deionised water Substances 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 26
- 238000005507 spraying Methods 0.000 claims description 24
- 229920001308 poly(aminoacid) Polymers 0.000 claims description 23
- 238000001291 vacuum drying Methods 0.000 claims description 22
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 241000272525 Anas platyrhynchos Species 0.000 claims description 16
- 239000006210 lotion Substances 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 13
- 239000004568 cement Substances 0.000 claims description 13
- 239000002131 composite material Substances 0.000 claims description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 13
- 159000000007 calcium salts Chemical class 0.000 claims description 12
- GCFHZZWXZLABBL-UHFFFAOYSA-N ethanol;hexane Chemical compound CCO.CCCCCC GCFHZZWXZLABBL-UHFFFAOYSA-N 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 11
- 238000012545 processing Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 150000003863 ammonium salts Chemical class 0.000 claims description 9
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 9
- 239000010931 gold Substances 0.000 claims description 9
- 229910052737 gold Inorganic materials 0.000 claims description 9
- 238000012805 post-processing Methods 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 238000010276 construction Methods 0.000 claims description 6
- 238000011065 in-situ storage Methods 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000003599 detergent Substances 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 239000004519 grease Substances 0.000 claims description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 16
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 8
- 238000004140 cleaning Methods 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 5
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 abstract description 4
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 abstract description 4
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 abstract description 4
- 230000002378 acidificating effect Effects 0.000 abstract description 4
- 235000001014 amino acid Nutrition 0.000 abstract description 4
- 150000001413 amino acids Chemical class 0.000 abstract description 4
- 235000003704 aspartic acid Nutrition 0.000 abstract description 4
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001506 calcium phosphate Substances 0.000 abstract description 4
- 229910000389 calcium phosphate Inorganic materials 0.000 abstract description 4
- 235000011010 calcium phosphates Nutrition 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 235000013922 glutamic acid Nutrition 0.000 abstract description 4
- 239000004220 glutamic acid Substances 0.000 abstract description 4
- 229910052588 hydroxylapatite Inorganic materials 0.000 abstract description 4
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 abstract description 4
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 abstract description 4
- 235000001968 nicotinic acid Nutrition 0.000 abstract description 2
- 229920002521 macromolecule Polymers 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 238000004381 surface treatment Methods 0.000 abstract 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 7
- 108010020346 Polyglutamic Acid Proteins 0.000 description 7
- 238000007654 immersion Methods 0.000 description 7
- 229920002643 polyglutamic acid Polymers 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 4
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- 230000002209 hydrophobic effect Effects 0.000 description 4
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 description 3
- 239000011538 cleaning material Substances 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
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- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 229910052586 apatite Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 210000001595 mastoid Anatomy 0.000 description 2
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241000254173 Coleoptera Species 0.000 description 1
- 229920001503 Glucan Polymers 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
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- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 108010000222 polyserine Proteins 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
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- 235000004400 serine Nutrition 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
Landscapes
- Surface Treatment Of Glass (AREA)
Abstract
The invention belongs to the technical fields of material science, bionics, nanometer technology and macromolecule science, speciafically a polyamino acid adjusted and controlled super-hydrophobic surface material constructed in a biomineralization way and the preparation method thereof. A glass pane after surface treatment is used as the base material; polyamino acid (acidic amino acid such as glutamic acid, aspartic acid andserine) is used as organic additives; and in a system added with inorganic minerals (calcium carbonate, calcium phosphate, hydroxyapatite, etc.), the surface with a micrometer-nanometer coarse structure is constructed on the original place of the glass pane with a biomineralization method. After treatment, the surface has an excellent super-hydrophobic performance. By adjusting the mineralization condition (the concentration of inorganic mineral salt and the concentration of organic additives), the morphology of the base surface can be controlled so that the super-hydrophobic state of the surface can be controlled in the end. The super-hydrophobic surface material has the advantages of easy preparation course, environment protection and controllable morphology. The super-hydrophobic surface material has great application prospect in many fields such as preparation of self-cleaning surfaces and anti-biological pollution coatings and the like.
Description
Technical field
The invention belongs to material science, bionics, nanometer technology and polymer science technical field, relate to a kind of material preparation method, the biomineralization that relates in particular to a kind of polyaminoacid regulation and control builds superhydrophobic surface material and preparation method; Meanwhile, the invention still further relates to a kind of superhydrophobic surface material that utilizes above-mentioned preparation method to make.
Background technology
Water droplet is greater than 150 ° and while being difficult for tumbling from surface, this surface of solids is considered to have super-hydrophobicity at the contact angle of the surface of solids.There are a large amount of peculiar natural super hydrophobic surfaces in nature, such as the shell of beetle in the leaf of paddy rice, desert, vola of the wing of butterfly and gecko etc.Along with the further investigation for these natural super-hydrophobic phenomenons and understanding, the combination that it is found that multistage coarse structure and low surface energy coat is the denominator of these super hydrophobic surfaces.A typical example being widely studied is lotus leaf surface, and unique self-cleaning function that it has is considered to jointly be given in conjunction with the wax-like coating of low-surface-energy by its surperficial micro-nano rough structure (the cilium shape material of micron-sized mastoid process and mastoid process nano surface level).Be subject to the inspiration of these natural super hydrophobic surfaces, people mainly can by increasing surperficial roughness and reducing its surface when realizing super hydrophobic surface, and then developed the method for the super hydrophobic surface based on the multistage coarse structure of preparation in a large number, comprising template, offset printing method, microballoon construction from part and phase separation method etc.But then, these preparation methods' complexity and triviality have limited their large-scale application.
As everyone knows, the natural minerals existing in nature, if shell, bone and tooth etc. are all the materials with complex topology structure and mechanical property excellence, they are under the regulation and control by large biological molecules such as protein, polypeptide and polysaccharide, to form under gentle condition.At present, the research of in-vitro simulated biomineralization concentrates on pattern and the crystal formation that utilizes various templates to regulate and control inorganic mineral mostly, people can easily obtain the various inorganic minerals with multilevel topology thus, but utilize these inorganic material with complex topology structure to come the research on constructing super-drainage surface also relatively less.The people such as Xiang utilize soluble starch for additive, and by controlling the concentration of starch solution, the concentration of calcium ion and pH value have prepared the calcium carbonate of various patterns, after it is carried out to metal spraying and lauryl mercaptan processing, can obtain close to super-hydrophobic surface.Similar with it, Wu etc. utilize glucan for organic formwork, by repeatedly depositing in glass pane surface, there is the brium carbonate of complex topography and prepared the surface with ultra-hydrophobicity through corresponding chemical processing, water droplet is greater than 150 ° at this lip-deep contact angle, and roll angle is less than 1 ° 18 '.These researchs show above, inorganic mineral is that natural sediment is on base material, active force between the two relatively a little less than, therefore cannot form stable functional surface, and author is not and the impact on final material wetability such as report crystal morphology, crystal formation and last handling process.
The present invention be take surface treated glass plate as base material, the polyaminoacid (acidic amino acid such as glutamic acid, aspartic acid, serine etc.) of take is organic additive, in adding inorganic mineral (calcium carbonate, calcium phosphate, hydroxyapatite etc.) system by biomineralization method in substrate of glass in-situ construction there is the surperficial of micro-nano rough structure, after metal spraying and chemical treatment, these surfaces present good ultra-hydrophobicity.We can be simply by regulating mineralising condition (concentration of inorganic mineral salinity and organic additive) to control the pattern of substrate surface the super-hydrophobic state of final control surface.The present invention has the super hydrophobic surface of multistage roughness method by biomineralization method preparation may have larger application prospect preparing aspect self-cleaning surface and stable against biological contamination coating.
Summary of the invention
Technical problem to be solved by this invention is: provide a kind of biomineralization based on polyaminoacid regulation and control to build the preparation method of superhydrophobic surface material; whole building-up process is simple and convenient; easy operating; with low cost; there is suitable feasibility and practical significance, can be large-scale production basis is provided.
In addition, the superhydrophobic surface material that the present invention also provides a kind of the present invention of utilization to make, it consists of the inorganic mineral that superficial growth has micro-nano different roughness, has superpower hydrophobic effect, can be for having self-cleaning material surface and bioantifouling aspect.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
A kind of biomineralization based on polyaminoacid regulation and control builds the preparation method of superhydrophobic surface material, take surface treated glass plate as base material, take polyaminoacid as organic additive, in being added with the system of inorganic mineral, by biomineralization method in substrate of glass in-situ construction there is the surface of micro-nano rough structure, after metal spraying and chemical treatment, these surfaces present good ultra-hydrophobicity;
Its preparation method comprises the following steps:
Step 1, glass pane surface, through the processing of ethanol-n-hexane, Cement Composite Treated by Plasma, repeatedly pretreatment of acid solution, are rinsed stand-by by deionized water repeatedly;
Step 2, will pretreated glass surface in step 1 be carried out to original position mineralising with inorganic calcium salt: will pretreated glass surface in step 1 be carried out to original position mineralising with inorganic calcium salt: the beaker of certain density calcium solution and soluble additive solution will be housed and the beaker of inorganic ammonium salt is housed, after sealing, stab respectively several duck eyes, put into a drier simultaneously, after reaction, take out glass plate and carry out post processing; After taking out glass plate, by deionized water, repeatedly rinse its surface, finally glass plate is carried out to vacuum drying;
Step 3, by the chemical treatment of carrying out of substrate surface after mineralising in step 2, and with absolute ethyl alcohol, glass pane surface is cleaned, finally by glass plate vacuum drying.
As a preferred embodiment of the present invention, in described step 1, it is with n-hexane, to wash after glass plate is washed with ethanol that ethanol-n-hexane is processed again, and then vacuum drying is stand-by.
As a preferred embodiment of the present invention, in described step 1, Cement Composite Treated by Plasma is that glass plate is washed to remove surperficial grease with liquid detergent, then uses Cement Composite Treated by Plasma 10s~5min, stand-by.
As a preferred embodiment of the present invention, in described step 1, acid solution comprises nitric acid washing lotion, concentrated sulfuric acid washing lotion;
It is that glass plate is put into after the nitric acid washing lotion preparing is soaked a few hours and taken out that nitric acid washing lotion is processed, and repeatedly rinses rear stand-by by deionized water;
It is that glass plate is put into after the concentrated sulfuric acid soaks the several seconds and taken out that the concentrated sulfuric acid is processed, and repeatedly rinses rear stand-by by deionized water.
As a preferred embodiment of the present invention, in described step 2, inorganic calcium salt and soluble additive are polyaminoacid.
As a preferred embodiment of the present invention, the temperature in described step 2 is 10~200 ℃, and the reaction time is 1~72h.
As a preferred embodiment of the present invention, washing described in described step 2 is for adopting deionized water washing, and washing times is 1-6 time.
As a preferred embodiment of the present invention, described in described step 2, be vacuum drying, its baking temperature is at 10-100 ℃, dry 1-48h.
As a preferred embodiment of the present invention, chemical treatment described in described step 3 is 1~300s containing the gold spraying instrument metal spraying time, then puts into positive lauryl mercaptan or 1H, 1H, 2H, the alcohol solution dipping of 2H-perfluor dodecyl mercaptans took out after a few hours, and the concentration of described ethanolic solution is 10
-6~10
-1mmol/L.
As a preferred embodiment of the present invention, in described step 3, by absolute ethyl alcohol and deionized water, wash, washing times is 1-6 time.
A superhydrophobic surface material that utilizes above-mentioned preparation method to make, described superhydrophobic surface material is the inorganic mineral that superficial growth has micro-nano different roughness.
Described method specifically comprises: for glass pane surface, ethanol-n-hexane, Cement Composite Treated by Plasma, the processing of nitric acid washing lotion, the concentrated sulfuric acid are processed, by deionized water, repeatedly rinsed stand-by.The certain density calcium chloride solution configuring and soluble additive (polyaminoacid) solution are added in the small beaker of 1~100mL, then the good little glass plate of previous processed is put into small beaker, after being sealed with parafilm sealed membrane, with pin, stab several duck eyes thereon.Again 1~100g inorganic ammonium salt is packed into another one small beaker equally with stabbing several duck eyes in the above after parafilm sealing.Beaker is above put into a drier simultaneously, and 10~200 ℃ of temperature, the reaction time is after 1~72h, to take out glass plate to carry out post processing.After taking out glass plate, by deionized water, repeatedly rinse its surface, washing times is 1-6 time, finally glass plate is carried out to vacuum drying.By long, there is the dry glass plate of inorganic calcium salt to put into gold spraying instrument metal spraying 1~300s, then put into positive lauryl mercaptan or 1H, 1H, 2H, the ethanolic solution (10 of 2H-perfluor dodecyl mercaptans
-6~10
-1mmol/L) immersion was taken out after a few hours, then with absolute ethyl alcohol, glass pane surface was cleaned, and washing times is 1-6 time, by glass plate vacuum drying.Finally adopt at 25 ℃, DataphysicsocA40 instrument test water at the contact angle of sample surfaces.
Beneficial effect of the present invention is: the biomineralization based on polyaminoacid regulation and control that the present invention proposes builds superhydrophobic surface material and preparation method thereof, provide and take surface treated glass plate as base material, with polyaminoacid (glutamic acid, aspartic acid, the acidic amino acids such as serine) be organic additive, be added with inorganic mineral (calcium carbonate, calcium phosphate, hydroxyapatite etc.) in system, by biomineralization method in substrate of glass in-situ construction there is the surface of micro-nano rough structure, after metal spraying and chemical treatment, these surfaces present good ultra-hydrophobicity.The present invention can be simply by regulating mineralising condition (concentration of inorganic mineral salinity and organic additive) to control the pattern of substrate surface the super-hydrophobic state of final control surface, preparation process is simple, environmental friendliness, efficient energy-saving, product size pattern is controlled.The method that the present invention has the super hydrophobic surface of multistage roughness by the preparation of biomineralization method will have larger application prospect in a plurality of fields such as preparing self-cleaning surface and stable against biological contamination coating.In addition, the superhydrophobic surface material that utilizes the present invention to make, it consists of the inorganic mineral that superficial growth has micro-nano different roughness, has superpower hydrophobic effect, can be for having self-cleaning material surface and bioantifouling aspect.
Accompanying drawing explanation
Fig. 1 is the electromicroscopic photograph of the pattern of the calcium carbonate of polyglutamic acid regulation and control lower glass plate Surface Creation in embodiment 1.
Fig. 2 prepares high resolution scanning Electronic Speculum figure in embodiment 3.
Fig. 3 be the surface of preparation in embodiment 3 after perfluor lauryl mercaptan is processed, water droplet is at its surperficial static contact angle schematic diagram.
The specific embodiment
Below in conjunction with accompanying drawing, describe the preferred embodiments of the present invention in detail.
Embodiment 1:
For glass pane surface, ethanol-n-hexane, Cement Composite Treated by Plasma, the processing of nitric acid washing lotion, the concentrated sulfuric acid are processed, by deionized water, are repeatedly rinsed stand-by.The calcium chloride solution of the 2mmol/L configuring and 0.5g/L polyglutamic acid solution are added in the small beaker of 10mL, then the good little glass plate of previous processed is put into small beaker, after being sealed with parafilm film, with pin, stab several duck eyes thereon.Again 10g inorganic ammonium salt is packed into another one small beaker equally with stabbing several duck eyes in the above after parafilm sealing.Beaker is above put into a drier simultaneously, and 25 ℃ of temperature, the reaction time is after 24h, to take out glass plate to carry out post processing.After taking out glass plate, by deionized water, repeatedly rinse its surface, washing times is 1-6 time, finally glass plate is carried out to vacuum drying.By long, there is the dry glass plate of inorganic calcium salt to put into gold spraying instrument metal spraying 30s, then put into positive lauryl mercaptan or 1H, 1H, 2H, the ethanolic solution (10 of 2H-perfluor dodecyl mercaptans
-3mmol/L) immersion was taken out after a few hours, then with absolute ethyl alcohol, glass pane surface was cleaned, and washing times is 1-6 time, finally by glass plate vacuum drying.Finally adopting test water at 25 ℃, DataphysicsocA40 instrument is 111 ± 2 ° at the contact angle of sample surfaces.
Fig. 1 is the electromicroscopic photograph of the pattern of the calcium carbonate of polyglutamic acid regulation and control lower glass plate Surface Creation in the present embodiment; In Fig. 1, when the calcium ion concentration of initial interpolation is very low (2mmol/L), the calcium carbonate granule negligible amounts and the skewness that in glass pane surface, generate, granule-morphology also has different, be mostly typical accurate dodecahedron, size is in 5 μ m left and right, and its part crystal face is relatively coarse.
The superhydrophobic surface material that utilizes the present invention to make, it consists of the inorganic mineral that growth has micro-nano different roughness, has superpower hydrophobic effect, can be for having self-cleaning material surface and bioantifouling aspect.
Embodiment 2:
For glass pane surface, ethanol-n-hexane, Cement Composite Treated by Plasma, the processing of nitric acid washing lotion, the concentrated sulfuric acid are processed, by deionized water, are repeatedly rinsed stand-by.The calcium chloride solution of the 5mmol/L configuring and 0.5g/L polyserine solution are added in the small beaker of 100mL, then the good little glass plate of previous processed is put into small beaker, after being sealed with parafilm film, with pin, stab several duck eyes thereon.Again 9g inorganic ammonium salt is packed into another one small beaker equally with stabbing several duck eyes in the above after parafilm sealing.Beaker is above put into a drier simultaneously, and 35 ℃ of temperature, the reaction time is after 48h, to take out glass plate to carry out post processing.After taking out glass plate, by deionized water, repeatedly rinse its surface, washing times is 1-6 time, finally glass plate is carried out to vacuum drying.By long, there is the dry glass plate of inorganic calcium salt to put into gold spraying instrument metal spraying 60s, then put into positive lauryl mercaptan or 1H, 1H, 2H, the ethanolic solution (10 of 2H-perfluor dodecyl mercaptans
-3mmol/L) immersion was taken out after a few hours, then with absolute ethyl alcohol, glass pane surface was cleaned, and washing times is 1-6 time, finally by glass plate vacuum drying.Finally adopting test water at 25 ℃, DataphysicsocA40 instrument is 151 ± 7 ° at the contact angle of sample surfaces.
Embodiment 3:
For glass pane surface, ethanol-n-hexane, Cement Composite Treated by Plasma, the processing of nitric acid washing lotion, the concentrated sulfuric acid are processed, by deionized water, are repeatedly rinsed stand-by.The calcium chloride of the 10mmol/L configuring and sodium dihydrogen phosphate and 0.6g/L polyglutamic acid solution are added in the small beaker of 100mL, then the good little glass plate of previous processed is put into small beaker, after being sealed with parafilm film, with pin, stab several duck eyes thereon.Again 8g inorganic ammonium salt is packed into another one small beaker equally with stabbing several duck eyes in the above after parafilm sealing.Beaker is above put into a drier simultaneously, and 30 ℃ of temperature, the reaction time is after 24h, to take out glass plate to carry out post processing.After taking out glass plate, by deionized water, repeatedly rinse its surface, washing times is 1-6 time, finally glass plate is carried out to vacuum drying.By long, there is the dry glass plate of inorganic calcium salt to put into gold spraying instrument metal spraying 80s, then put into positive lauryl mercaptan or 1H, 1H, 2H, the ethanolic solution (10 of 2H-perfluor dodecyl mercaptans
-2mmol/L) immersion was taken out after a few hours, then with absolute ethyl alcohol, glass pane surface was cleaned, and washing times is 1-6 time, finally by glass plate vacuum drying.Finally adopting test water at 25 ℃, DataphysicsocA40 instrument is 151 ± 2 ° at the contact angle of sample surfaces.
Fig. 2 prepares high resolution scanning Electronic Speculum figure in the present embodiment, have Fig. 2 to see, the great amount of hydroxy group apatite that glass sheet substrate surface exists is the spheric granules that diameter 3 μ m and surface are needle-like hair thorn-like.
Fig. 3 be the surface of preparing in the present embodiment after perfluor lauryl mercaptan is processed, water droplet is at its surperficial static contact angle schematic diagram; In Fig. 3, the length obtaining has the glass baseplate surface of great amount of hydroxy group apatite spheric granules after certain chemical treatment, to have equally preferably hydrophobic performance, even if for the liquid of large volume, still keeps higher static contact angle.
Embodiment 4:
For glass pane surface, ethanol-n-hexane, Cement Composite Treated by Plasma, the processing of nitric acid washing lotion, the concentrated sulfuric acid are processed, by deionized water, are repeatedly rinsed stand-by.The calcium chloride solution of the 20mmol/L configuring and 0.8g/L polyglutamic acid solution are added in the small beaker of 10mL, then the good little glass plate of previous processed is put into small beaker, after being sealed with parafilm film, with pin, stab several duck eyes thereon.Again 10g inorganic ammonium salt is packed into another one small beaker equally with stabbing several duck eyes in the above after parafilm sealing.Beaker is above put into a drier simultaneously, and 20 ℃ of temperature, the reaction time is after 24h, to take out glass plate to carry out post processing.After taking out glass plate, by deionized water, repeatedly rinse its surface, washing times is 1-6 time, finally glass plate is carried out to vacuum drying.By long, there is the dry glass plate of inorganic calcium salt to put into gold spraying instrument metal spraying 100s, then put into positive lauryl mercaptan or 1H, 1H, 2H, the ethanolic solution (~10 of 2H-perfluor dodecyl mercaptans
-1mmol/L) immersion was taken out after a few hours, then with absolute ethyl alcohol, glass pane surface was cleaned, and washing times is 1-6 time, finally by glass plate vacuum drying.Finally adopting test water at 25 ℃, DataphysicsocA40 instrument is 158 ± 4 ° at the contact angle of sample surfaces.
Embodiment 5:
For glass pane surface, ethanol-n-hexane, Cement Composite Treated by Plasma, the processing of nitric acid washing lotion, the concentrated sulfuric acid are processed, by deionized water, are repeatedly rinsed stand-by.The calcium chloride solution of the 20mmol/L configuring and 0.2g/L polyglutamic acid solution are added in the small beaker of 50mL, then the good little glass plate of previous processed is put into small beaker, after being sealed with parafilm film, with pin, stab several duck eyes thereon.Again 10g inorganic ammonium salt is packed into another one small beaker equally with stabbing several duck eyes in the above after parafilm sealing.Beaker is above put into a drier simultaneously, and 10 ℃ of temperature, the reaction time is after 36h, to take out glass plate to carry out post processing.After taking out glass plate, by deionized water, repeatedly rinse its surface, washing times is 1-6 time, finally glass plate is carried out to vacuum drying.By long, there is the dry glass plate of inorganic calcium salt to put into gold spraying instrument metal spraying 90s, then put into positive lauryl mercaptan or 1H, 1H, 2H, the ethanolic solution (~10 of 2H-perfluor dodecyl mercaptans
-3mmol/L) immersion was taken out after a few hours, then with absolute ethyl alcohol, glass pane surface was cleaned, and washing times is 1-6 time, finally by glass plate vacuum drying.Finally adopting test water at 25 ℃, DataphysicsocA40 instrument is 153 ± 3 ° at the contact angle of sample surfaces.
Embodiment 6:
For glass pane surface, ethanol-n-hexane, Cement Composite Treated by Plasma, the processing of nitric acid washing lotion, the concentrated sulfuric acid are processed, by deionized water, are repeatedly rinsed stand-by.The calcium chloride solution of the 20mmol/L configuring and 0.05g/L polyglutamic acid solution are added in the small beaker of 10mL, then the good little glass plate of previous processed is put into small beaker, after being sealed with parafilm film, with pin, stab several duck eyes thereon.Again 10g inorganic ammonium salt is packed into another one small beaker equally with stabbing several duck eyes in the above after parafilm sealing.Beaker is above put into a drier simultaneously, and 30 ℃ of temperature, the reaction time is after 36h, to take out glass plate to carry out post processing.After taking out glass plate, by deionized water, repeatedly rinse its surface, washing times is 1-6 time, finally glass plate is carried out to vacuum drying.By long, there is the dry glass plate of inorganic calcium salt to put into gold spraying instrument metal spraying 120s, then put into positive lauryl mercaptan or 1H, 1H, 2H, the ethanolic solution (~10 of 2H-perfluor dodecyl mercaptans
-4mmol/L) immersion was taken out after a few hours, then with absolute ethyl alcohol, glass pane surface was cleaned, and washing times is 1-6 time, finally by glass plate vacuum drying.Finally adopting test water at 25 ℃, DataphysicsocA40 instrument is 135 ± 7 ° at the contact angle of sample surfaces.
In sum, the biomineralization based on polyaminoacid regulation and control that the present invention proposes builds the preparation method of superhydrophobic surface material, provide and take surface treated glass plate as base material, with polyaminoacid (glutamic acid, aspartic acid, the acidic amino acids such as serine) be organic additive, be added with inorganic mineral (calcium carbonate, calcium phosphate, hydroxyapatite etc.) in system, by biomineralization method in substrate of glass in-situ construction there is the surface of micro-nano rough structure, after metal spraying and chemical treatment, these surfaces present good ultra-hydrophobicity.The present invention can be simply by regulating mineralising condition (concentration of inorganic mineral salinity and organic additive) to control the pattern of substrate surface the super-hydrophobic state of final control surface, preparation process is simple, environmental friendliness, efficient energy-saving, product size pattern is controlled.The method that the present invention has the super hydrophobic surface of multistage roughness by the preparation of biomineralization method will have larger application prospect in a plurality of fields such as preparing self-cleaning surface and stable against biological contamination coating.
Here description of the invention and application is illustrative, not wants by scope restriction of the present invention in the above-described embodiments.Here the distortion of disclosed embodiment and change is possible, and for those those of ordinary skill in the art, the various parts of the replacement of embodiment and equivalence are known.Those skilled in the art are noted that in the situation that not departing from spirit of the present invention or substantive characteristics, and the present invention can be with other form, structure, layout, ratio, and realizes with other assembly, material and parts.In the situation that not departing from the scope of the invention and spirit, can carry out other distortion and change to disclosed embodiment here.
Claims (10)
1. the biomineralization of polyaminoacid regulation and control builds a preparation method for superhydrophobic surface material, it is characterized in that:
Take surface treated glass plate as base material, take polyaminoacid as organic additive, in being added with the system of inorganic mineral, by biomineralization method in substrate of glass in-situ construction there is the surface of micro-nano rough structure, after metal spraying and chemical treatment, these surfaces present good ultra-hydrophobicity;
Its preparation method comprises the following steps:
Step 1, glass pane surface, through the processing of ethanol-n-hexane, Cement Composite Treated by Plasma, repeatedly pretreatment of acid solution, are rinsed stand-by by deionized water repeatedly;
Step 2, will pretreated glass surface in step 1 be carried out to original position mineralising with inorganic calcium salt: the beaker of certain density calcium solution and soluble additive solution will be housed and the beaker of inorganic ammonium salt is housed, after sealing, stab respectively several duck eyes, put into a drier simultaneously, after reaction, take out glass plate and carry out post processing; After taking out glass plate, by deionized water, repeatedly rinse its surface, finally glass plate is carried out to vacuum drying;
Step 3, by the chemical treatment of carrying out of substrate surface after mineralising in step 2, and with absolute ethyl alcohol, glass pane surface is cleaned, finally by glass plate vacuum drying.
2. the biomineralization based on polyaminoacid regulation and control according to claim 1 builds the preparation method of superhydrophobic surface material, it is characterized in that:
In described step 1, it is with n-hexane, to wash after glass plate is washed with ethanol that ethanol-n-hexane is processed again, and then vacuum drying is stand-by.
3. the biomineralization based on polyaminoacid regulation and control according to claim 1 builds the preparation method of superhydrophobic surface material, it is characterized in that:
In described step 1, Cement Composite Treated by Plasma is that glass plate is washed to remove surperficial grease with liquid detergent, then uses Cement Composite Treated by Plasma 10s~5min, stand-by.
4. the biomineralization based on polyaminoacid regulation and control according to claim 1 builds the preparation method of superhydrophobic surface material, it is characterized in that:
In described step 1, acid solution comprises nitric acid washing lotion, concentrated sulfuric acid washing lotion;
It is that glass plate is put into after the nitric acid washing lotion preparing is soaked a few hours and taken out that nitric acid washing lotion is processed, and repeatedly rinses rear stand-by by deionized water;
It is that glass plate is put into after the concentrated sulfuric acid soaks the several seconds and taken out that the concentrated sulfuric acid is processed, and repeatedly rinses rear stand-by by deionized water.
5. the biomineralization based on polyaminoacid regulation and control according to claim 1 builds the preparation method of superhydrophobic surface material, it is characterized in that:
In described step 2, inorganic calcium salt and soluble additive are polyaminoacid.
6. the biomineralization based on polyaminoacid regulation and control according to claim 1 builds the preparation method of superhydrophobic surface material, it is characterized in that:
Temperature in described step 2 is 10~200 ℃, and the reaction time is 1~72h.
7. the biomineralization based on polyaminoacid regulation and control according to claim 1 builds the preparation method of superhydrophobic surface material, it is characterized in that:
Washing described in described step 2 is for adopting deionized water washing, and washing times is 1~6 time.
8. the biomineralization based on polyaminoacid regulation and control according to claim 1 builds the preparation method of superhydrophobic surface material, it is characterized in that:
Described in described step 2, be that vacuum drying baking temperature is at 10~100 ℃, dry 1~48h.
9. the biomineralization based on polyaminoacid regulation and control according to claim 1 builds the preparation method of superhydrophobic surface material, it is characterized in that:
In described step 3, by absolute ethyl alcohol and deionized water, wash, washing times is 1~6 time;
Chemical treatment described in described step 3 is 1~300s containing the gold spraying instrument metal spraying time, then puts into positive lauryl mercaptan or 1H, 1H, and 2H, the alcohol solution dipping of 2H-perfluor dodecyl mercaptans took out after a few hours, and the concentration of described ethanolic solution is 10
-6~10
-1mmol/L.
10. a superhydrophobic surface material that utilizes the described preparation method of one of claim 1 to 9 to make, is characterized in that: described superhydrophobic surface material is the inorganic mineral that superficial growth has micro-nano different roughness.
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KR20090039179A (en) * | 2007-10-17 | 2009-04-22 | 엘지마이크론 주식회사 | Superhydrophobic film and the method thereof |
CN101942654A (en) * | 2010-10-27 | 2011-01-12 | 东南大学 | Method for immersing superhydrophobic surface of aluminum alloy in one step |
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2013
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Publication number | Priority date | Publication date | Assignee | Title |
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KR20090039179A (en) * | 2007-10-17 | 2009-04-22 | 엘지마이크론 주식회사 | Superhydrophobic film and the method thereof |
CN101942654A (en) * | 2010-10-27 | 2011-01-12 | 东南大学 | Method for immersing superhydrophobic surface of aluminum alloy in one step |
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HENG CAO ET AL.: "Fabrication of superhydrophobic surfaces via CaCO3 mineralization mediated by poly(glutamic acid)", 《JOURNAL OF SOLID STATE CHEMISTRY》 * |
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